Thermosetting polyurethane material for a golf ball cover

ABSTRACT

A curative blend for a thermosetting polyurethane material that allows for a polyurethane material with greater durability is disclosed herein. The curative blend is composed of 4,4′-methylenebis-(2,6-diethyl)-aniline and a second curing agent selected from the group consisting of N,N′-bis-alkyl-p-phenylenediamine, N,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediamine and an aliphatic diamine. A preferred polyurethane prepolymer is polytetramethylene ether glycol terminated toluene diisocyanate prepolymer. The thermosetting polyurethane is preferably utilized as a cover for a golf ball. The cover is preferably formed over a core and boundary layer.

CROSS REFERENCES TO RELATED APPLICATIONS

The Present Application is a continuation-in-part application of U.S.patent application Ser. No. 10/064,721, filed on Aug. 9, 2002, now U.S.Pat. No. 6,787,626, which is a continuation-in-part application of U.S.patent application Ser. No. 10/063,979, filed on May 31, 2002, nowabandoned.

FEDERAL RESEARCH STATEMENT

[Not Applicable]

BACKGROUND OF INVENTION

1. Field of the Invention

The present invention relates to a thermosetting polyurethane material.More specifically, the present invention relates to a thermosettingpolyurethane material for a cover of a golf ball.

2. Description of the Related Art

Conventionally golf balls are made by molding a cover around a core. Thecore may be wound or solid. A wound core typically comprises elasticthread wound about a solid or liquid center. Unlike wound cores, solidcores do not include a wound elastic thread layer. Solid cores typicallymay comprise a single solid piece center or a solid center covered byone or more mantle or boundary layers of material.

The cover may be injection molded, compression molded, or cast over thecore. Injection molding typically requires a mold having at least onepair of mold cavities, e.g., a first mold cavity and a second moldcavity, which mate to form a spherical recess. In addition, a mold mayinclude more than one mold cavity pair.

In one exemplary injection molding process each mold cavity may alsoinclude retractable positioning pins to hold the core in the sphericalcenter of the mold cavity pair. Once the core is positioned in the firstmold cavity, the respective second mold cavity is mated to the first toclose the mold. A cover material is then injected into the closed mold.The positioning pins are retracted while the cover material is flowableto allow the material to fill in any holes caused by the pins. When thematerial is at least partially cured, the covered core is removed fromthe mold.

As with injection molding, compression molds typically include multiplepairs of mold cavities, each pair comprising first and second moldcavities that mate to form a spherical recess. In one exemplarycompression molding process, a cover material is pre-formed intohalf-shells, which are placed into a respective pair of compression moldcavities. The core is placed between the cover material half-shells andthe mold is closed. The core and cover combination is then exposed toheat and pressure, which cause the cover half-shells to combine and forma full cover.

As with the above-referenced processes, a casting process also utilizespairs of mold cavities. In a casting process, a cover material isintroduced into a first mold cavity of each pair. Then, a core is heldin position (e.g. by an overhanging vacuum or suction apparatus) tocontact the cover material in what will be the spherical center of themold cavity pair. Once the cover material is at least partially cured(e.g., a point where the core will not substantially move), the core isreleased, the cover material is introduced into a second mold cavity ofeach pair, and the mold is closed. The closed mold is then subjected toheat and pressure to cure the cover material thereby forming a cover onthe core. With injection molding, compression molding, and casting, themolding cavities typically include a negative dimple pattern to impart adimple pattern on the cover during the molding process.

Materials previously used as golf ball covers include balata (natural orsynthetic), gutta-percha, ionomeric resins (e.g., DuPont's SURLYN®), andpolyurethanes. Balata is the benchmark cover material with respect tosound (i.e. the sound made when the ball is hit by a golf club) and feel(i.e. the sensation imparted to the golfer when hitting the ball).Natural balata is derived from the Bully Gum tree, while syntheticbalata is derived from a petroleum compound. Balata is expensivecompared to other cover materials, and golf balls covered with balatatend to have poor durability (i.e. poor cut and shear resistance). Guttapercha is derived from the Malaysian sapodilla tree. A golf ball coveredwith gutta percha is considered to have a harsh sound and feel ascompared to balata covered golf balls.

Ionomeric resins, as compared to balata, are typically less expensiveand tend to have good durability. However, golf balls having ionomericresin covers typically have inferior sound and feel, especially ascompared to balata covers.

A golf ball with a polyurethane cover generally has greater durabilitythan a golf ball with a balata cover. The polyurethane covered golf ballgenerally has a better sound and feel than a golf ball with an ionomericresin cover. Polyurethanes may be thermoset or thermoplastic.Polyurethanes are formed by reacting a prepolymer with a polyfunctionalcuring agent, such as a polyamine or a polyol. The polyurethaneprepolymer is the reaction product of, for example, a diisocyanate and apolyol such as a polyether or a polyester. Several patents describe theuse of polyurethanes in golf balls. However, golf balls withpolyurethane covers usually do not have the distance of other golf ballssuch as those with covers composed of SURLYN® materials.

Gallagher, U.S. Pat. No. 3,034,791 discloses a polyurethane golf ballcover prepared from the reaction product of poly(tetramethylene ether)glycol and toluene-2,4-diisocyanates (TDI), either pure TDI or anisomeric mixture.

Isaac, U.S. Pat. No. 3,989,568 (the '568 patent) discloses apolyurethane golf ball cover prepared from prepolymers and curing agentsthat have different rates of reaction so a partial cure can be made. The'568 patent explains that “the minimum number of reactants is three.”Specifically, in '568 patent, two or more polyurethane prepolymers arereacted with at least one curing agent, or at least one polyurethaneprepolymer is reacted with two or more curing agents as long as thecuring agents have different rates of reaction. The '568 patent alsoexplains that “[o]ne of the great advantages of polyurethane covers madein accordance with the instant invention is that they may be made verythin . . . ”, and “[t]here is no limitation on how thick the cover ofthe present invention may be but it is generally preferred . . . thatthe cover is no more than about 0.6 inches in thickness.” The examplesin the '568 patent only disclose golf balls having covers that are about0.025 inches thick.

Similar to Isaac, PCT International Publication Number WO 99/43394 toDunlop Maxfli Sports Corporation, discloses using two curing agents tocontrol the reaction time for polyurethane formation. The two curingagents are a dimethylthio 2,4-toluenediamine and diethyl2,4-toluenediamine, which are blended to control the reaction rate of atoluene diisocyanate based polyurethane prepolymer or a4,4′-diphenylmethane diisocyanate based polyurethane prepolymer.

Dusbiber, U.S. Pat. No. 4,123,061 (the '061 patent) discloses apolyurethane golf ball cover prepared from the reaction product of apolyether, a diisocyanate and a curing agent. The '061 patent disclosesthat the polyether may be polyalkylene ether glycol orpolytetramethylene ether glycol. The '061 patent also discloses that thediisocyanate may be TDI, 4,4′-diphenylmethane diisocyanate (“MDI”), and3,3′-dimethyl-4,4′-biphenylene diisocyanate (“TODI”). Additionally, the'061 patent discloses that the curing agent may be either a polyol(either tri- or tetra-functional and not di-functional) such astriisopropanol amine (“TIPA”) or trimethoylol propane (“TMP”), or anamine-type having at least two reactive amine groups such as:3,3′dichlorobenzidene; 3,3′dichlorobenzidene; 3,3′dichloro 4,4′diaminodiphenyl methane (“MOCA”); N,N,N′,N′ tetrakis (2-hydroxy propyl)ethylene diamine; or Uniroyal's Curalon L which is an aromatic diaminemixture.

Hewitt, et al., U.S. Pat. No. 4,248,432 (the '432 patent) discloses athermoplastic polyesterurethane golf ball cover formed from a reactionproduct of a polyester glycol (molecular weight of 800–1500) (aliphaticdiol and an aliphatic dicarboxylic acid) with a para-phenylenediisocyanate (“PPDI”) or cyclohexane diisocyanate in the substantialabsence of curing or crosslinking agents. The '432 patent teachesagainst the use of chain extenders in making polyurethanes. The '432patent states, “when small amounts of butanediol-1,4 are mixed with apolyester . . . the addition results in polyurethanes that do not havethe desired balance of properties to provide good golf ball covers.Similarly, the use of curing or crosslinking agents is not desired . . .”.

Holloway, U.S. Pat. No. 4,349,657 (the '657 patent) discloses a methodfor preparing polyester urethanes with PPDI by reacting a polyester(e.g. prepared from aliphatic glycols having 2–8 carbons reacted withaliphatic dicarboxylic acids having 4–10 carbons) with a molar excess ofPPDI to obtain an isocyanate-terminated polyester urethane (in liquidform and stable at reaction temperatures), and then reacting thepolyester urethane with additional polyester. The '657 patent claimsthat the benefit of this new process is the fact that a continuouscommercial process is possible without stability problems. The '657patent further describes a suitable use for the resultant material to begolf ball covers.

Wu, U.S. Pat. No. 5,334,673 (the '673 patent) discloses a polyurethaneprepolymer cured with a slow-reacting curing agent selected fromslow-reacting polyamine curing agents and difunctional glycols (i.e.,3,5-dimethylthio-2,4-toluenediamine,3,5-dimethylthio-2,6-toluenediamine, N,N′-dialkyldiamino diphenylmethane, trimethyleneglycol-di-p-aminobenzoate,polytetramethyleneoxide-di-p-aminobenzoate, 1,4-butanediol,2,3-butanediol, 2,3-dimethyl-2,3-butanediol, ethylene glycol, andmixtures of the same). The polyurethane prepolymer in the '673 patent isdisclosed as made from a polyol (e.g., polyether, polyester, orpolylactone) and a diisocyanate such as MDI or TODI. The polyetherpolyols disclosed in the '673 patent are polytetramethylene etherglycol, poly(oxypropylene) glycol, and polybutadiene glycol. Thepolyester polyols disclosed in the '673 patent are polyethylene adipateglycol, polyethylene propylene adipate glycol, and polybutylene adipateglycol. The polylactone polyols disclosed in the '673 patent arediethylene glycol initiated caprolactone, 1,4-butanediol initiatedcaprolactone, trimethylol propane initiated caprolactone, and neopentylglycol initiated caprolactone.

Cavallaro, et al., U.S. Pat. No. 5,688,191 discloses a golf ball havingcore, mantle layer and cover, wherein the mantle layer is either avulcanized thermoplastic elastomer, functionalized styrene-butadieneelastomer, thermoplastic polyurethane, metallocene polymer or blends ofthe same and thermoset materials.

Wu, et al., U.S. Pat. No. 5,692,974 discloses golf balls having coversand cores that incorporate urethane ionomers (i.e. using an alkylatingagent to introduce ionic interactions in the polyurethane and therebyproduce cationic type ionomers).

Sullivan, et al., U.S. Pat. No. 5,803,831 (the '831 patent) discloses agolf ball having a multi-layer cover wherein the inner cover layer has ahardness of at least 65 Shore D and the outer cover layer has a hardnessof 55 Shore D or less, and more preferably 48 Shore D or less. The '831patent explains that this dual layer construction provides a golf ballhaving soft feel and high spin on short shots, and good distance andaverage spin on long shots. The '831 patent provides that the innercover layer can be made from high or low acid ionomers such as SURLYN®,ESCOR® or IOTEK®, or blends of the same, nonionomeric thermoplasticmaterial such as metallocene catalyzed polyolefins or polyamides,polyamide/ionomer blends, polyphenylene ether/ionomer blends, etc.,(having a Shore D hardness of at least 60 and a flex modulus of morethan 30000 psi), thermoplastic or thermosetting polyurethanes, polyesterelastomers (e.g. HYTREL®), or polyether block amides (e.g. PEBAX®), orblends of these materials. The '831 patent also provides that the outercover layer can be made from soft low modulus (i.e. 1000–10000 psi)material such as low-acid ionomers, ionomeric blends, non-ionomericthermoplastic or thermosetting materials such as polyolefins,polyurethane (e.g. thermoplastic polyurethanes like TEXIN®, PELETHANE®,and thermoset polyurethanes like those disclosed in Wu, U.S. Pat. No.5,334,673), polyester elastomer (e.g. HYTREL®), or polyether block amide(e.g. PEBAX®), or a blend of these materials.

Hebert, et al., U.S. Pat. No. 5,885,172 (the '172 patent) discloses amultilayer golf ball giving a “progressive performance” (i.e. differentperformance characteristics when struck with different clubs atdifferent head speeds and loft angles) and having an outer cover layerformed of a thermoset material with a thickness of less than 0.05 inchesand an inner cover layer formed of a high flexural modulus material. The'172 patent provides that the outer cover is made from polyurethaneionomers as described in Wu, et al., U.S. Pat. No. 5,692,974, orthermoset polyurethanes such as TDI or methylenebis-(4-cyclohexylisocyanate) (“HMDI”), or a polyol cured with a polyamine (e.g.methylenedianiline (MDA), or with a trifunctional glycol (e.g.,N,N,N′,N′-tetrakis(2-hydroxpropyl)ethylenediamine). The '172 alsoprovides that the inner cover has a Shore D hardness of 65–80, aflexural modulus of at least about 65,000 psi, and a thickness of about0.020–0.045 inches. Exemplary materials for the inner cover areionomers, polyurethanes, polyetheresters (e.g. HYTREL®), polyetheramides(e.g., PEBAX®), polyesters, dynamically vulcanized elastomers,functionalized styrene-butadiene elastomer, metallocene polymer, blendsof these materials, nylon or acrylonitrile-butadiene-styrene copolymer.

Wu, U.S. Pat. No. 5,484,870 (the '870 patent) discloses golf ballshaving covers composed of a polyurea composition. The polyureacomposition disclosed in the '870 patent is a reaction product of anorganic isocyanate having at least two functional groups and an organicamine having at least two functional groups. One of the organicisocyanates disclosed by the '870 patent is PPDI.

Although the prior art has disclosed golf ball covers composed of manydifferent polyurethane materials, none of these golf balls have provencompletely satisfactory. Dissatisfaction, for example, remains withprocessing and manufacturing the balls, especially with controlling thereaction time of the curative and prepolymer. If the “gel time” forformation of a polyurethane material is too fast, the time to place acore in a hemispherical cavity with the gelling pre-polyurethanematerial and to mate the hemispherical cavity with a correspondinghemispherical cavity is greatly reduced thereby leading to processingproblems like air pockets, and centering of the core.

SUMMARY OF INVENTION

The present invention is a more durable polyurethane material for a golfball cover. One aspect of the present invention is a polyurethanematerial formed from at least one polyurethane prepolymer and curativeblend composed of 4,4′-methylenebis-(2,6-diethyl)-aniline and a secondcuring agent selected from the group consisting ofN,N′-bis-alkyl-p-phenylenediamine, N,N′-dialkylamino-diphenylmethanewith tetrapropoxylated ethylenediamine and an aliphatic diamine.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates a perspective view of a golf ball of the presentinvention including a cut-away portion showing a core, a boundary layer,and a cover.

FIG. 2 illustrates a perspective view of a golf ball of the presentinvention including a cut-away portion core and a cover.

DETAILED DESCRIPTION

As illustrated in FIG. 1, a golf ball is generally indicated as 10. Thegolf ball 10 preferably includes a core 12, a boundary layer 14 and acover 16. Alternatively, as shown in FIG. 2, the golf ball 10 may onlyinclude a core 12 and a cover 16. The cover 16 is composed of athermosetting polyurethane material of the present invention. In apreferred embodiment, the cover 16 is formed over a boundary layer 14and core 12, as shown in FIG. 1. Alternatively, the cover 16 is formedover the core 12, as shown in FIG. 2. Those skilled in the art willrecognize that the core may be solid, hollow, multi-piece orliquid-filled, the boundary layer may be partitioned into additionallayers, and the golf ball may have a wound layer without departing fromthe scope and spirit of the present invention.

The polyurethane material of the present invention is formed fromreactants comprising at least one polyurethane prepolymer and a curativecomprising a 4,4′-methylenebis-(2,6-diethyl)-aniline. The4,4′-methylenebis-(2,6-diethyl)-aniline is preferably present in anamount of 10 to 90 parts per one hundred parts of the curative blend,more preferably in an amount of 25 to 75 parts per one hundred parts ofthe curative blend, yet more preferably 30 to 70 parts per one hundredparts of the curative blend, even more preferably 35 to 65 parts per onehundred parts of the curative blend, and most preferably 50 parts perone hundred parts of the curative blend. The4,4′-methylenebis-(2,6-diethyl)-aniline has an equivalent weight of 155,and a molecular weight of 310. A preferred4,4′-methylenebis-(2,6-diethyl)-aniline is available from LONZAGROUPunder the brand name LONZACURE M-DEA.

A preferred second curative component of a curative blend used in apolyurethane material of the present invention is preferablyN,N′-bis-alkyl-p-phenylenediamine, N,N′-dialkylamino-diphenylmethanewith tetrapropoxylated ethylenediamine or an aliphatic diamine.

The second curative component is preferably present in an amount of 10to 90 parts per one hundred parts of the curative blend, more preferably25 to 75 parts per one hundred parts of the curative blend, yet morepreferably 30 to 70 parts per one hundred parts of the curative blend,even more preferably 35 to 65 parts per one hundred parts of thecurative blend, and most preferably 50 parts per one hundred parts ofthe curative blend. A preferred N,N′-bis-alkyl-p-phenylenediamine isavailable from UOP Company under the brand name UNILINK 4100. Apreferred N,N′-dialkylamino-diphenylmethane with tetrapropoxylatedethylenediamine is available from UOP Company under the brand nameUNILINK 4230. A preferred aliphatic diamine is available from UOPCompany under the brand name C-1000.

The N,N′-bis-alkyl-p-phenylenediamine andN,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediamineare aromatic secondary diamine chain extenders for polyurethanepolymers, and each has a slower rate of reaction than conventionalaromatic amines. When used in a curative blend, theN,N′-bis-alkyl-p-phenylenediamine or the N,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediamine slows the reaction andlowers the temperature of the reaction. TheN,N′-bis-alkyl-p-phenylenediamine has an equivalent weight of 110, and amolecular weight of 220. The N,N′-dialkylamino-diphenylmethane withtetrapropoxylated ethylenediamine has an equivalent weight of 130, and amolecular weight of 260.

The polyurethane prepolymer is preferably selected from toluenediisocyanate-based polyurethane prepolymers, para-phenylenediisocyanate-based polyurethane prepolymers, 1,6,hexamethylene-diisocyanate based polyurethane prepolymers, and4,4′-diphenylmethane diisocyanate-based polyurethane prepolymers. Thepolyurethane prepolymer is preferably utilized alone or in a blend oftwo or three polyurethane prepolymers.

The polyurethane prepolymer is most preferably a toluenediisocyanate-based polyurethane prepolymer such as a polypropyleneglycol terminated toluene diisocyanate prepolymer or apolytetramethylene ether glycol terminated toluene diisocyanateprepolymer, both aromatic polyurethane prepolymers. A preferredpolypropylene glycol terminated toluene diisocyanate prepolymer isavailable from Uniroyal Chemical Company of Middlebury, Conn., under thetradename ADIPRENE® LFG960. A preferred polytetramethylene ether glycolterminated toluene diisocyanate prepolymer (NCO content 5%) is availablefrom Uniroyal Chemical Company of Middlebury, Conn., under the tradenameADIPRENE® LF930. Another toluene diisocyanate prepolymer is apolytetramethylene ether glycol terminated toluene diisocyanateprepolymer (NCO content 6%) available from Uniroyal Chemical Company ofMiddlebury, Conn., under the tradename ADIPRENE® LF950. The use ofmultiple polyurethane prepolymers is set forth in U.S. Pat. No.6,190,268, entitled Golf Ball With A Polyurethane Cover, filed on Jul.27, 1999, assigned to Callaway Golf Company, and which is herebyincorporated by reference in its entirety.

An alternative polyurethane prepolymer is a para-phenylenediisocyanate-based polyurethane prepolymer such as para-phenylenediisocyanate terminated polyester prepolymer, which is available fromUniroyal Chemical under the tradename ADIPRENE® LFPX 2950, orpara-phenylene diisocyanate terminated polyether prepolymer, which isavailable from Uniroyal Chemical under the tradename ADIPRENE® LFPX 950.

Other preferred polyurethane prepolymers are the polytetramethyleneether glycol terminated hexamethylene diisocyanate prepolymers availablefrom Uniroyal Chemical under the tradename ADIPRENE® LFH750, ADIPRENE®LFH749 and ADIPRENE® LFH720, which are aliphatic polyurethaneprepolymers.

The ratio of the polyurethane prepolymer to curative is determined bythe nitrogen-carbon-oxygen group (“NCO”) content of the polyurethaneprepolymer. For example, the NCO content of the polypropylene glycolterminated toluene diisocyanate prepolymer is preferably in the range of3.0% to 6.0%, more preferably in the range of 4.0% to 5.75%, and mostpreferably 5.70%. The NCO content of the polytetramethylene ether glycolterminated toluene diisocyanate prepolymer is preferably in the range of3.75% to 7.0%, more preferably in the range of 4.0% to 6.5%, and mostpreferably 5% or 6%. The weight ratio of the polyurethane prepolymer tothe curative is preferably in the range of about 10:1 to about 30:1. TheNCO content of the polytetramethylene ether glycol terminatedhexamethylene diisocyanate prepolymer is preferably in the range of 8.0%to 12.0%, more preferably in the range of 10.0% to 11.5%, and mostpreferably 11%.

Prior to curing, the polyurethane prepolymer and curative blend arepreferably stored separately. In general, the polyurethane material isformed by first heating and mixing the curative blend. Then, thepolyurethane prepolymer and the curative blend are mixed in a chamber.The mixture from the chamber is dispensed into a hemispherical cavityprior to insertion of a golf ball precursor product. Thepre-polyurethane material is cured by applying heat and pressure for apredetermined time period. A more specific process is set forth below.

The polyurethane prepolymer is preferably degassed and warmed in a firstholding container. The processing temperature for the polyurethaneprepolymer is preferably in the range of about 70–130° F., and mostpreferably in the range of about 80–120° F. The polyurethane prepolymeris preferably flowable from the first holding container to a mixingchamber in a range of about 200–1100 grams of material per minute, or asneeded for processing. In addition, the polyurethane prepolymer may beagitated in the first holding container, in the range of 0–250 rpm, tomaintain a more even distribution of material and to eliminatecrystallization.

The curative blend is degassed and warmed in a second holding container.The processing temperature for the curative blend is preferably in therange of about 50–230° F., and more preferably in the range of about80–210° F., and most preferably in the range of about 170–190° F. Thecurative is preferably flowable from the second holding container to themixing chamber in the range of about 15–75 grams of material per minute,or as needed. Additives may be added to the curative blend as desired.

The polyurethane prepolymer and curative blend are preferably added tothe common mixing chamber at a temperature in the range of about160–220° F. A colorant material, such as, for example, titanium dioxide,barium sulfate, and/or zinc oxide in a glycol or castor oil carrier,and/or other additive material(s) as are well known in the art, may beadded to the common mixing chamber. The amount of colorant materialadded is preferably in the range of about 0–10% by weight of thecombined polyurethane prepolymer and curative materials, and morepreferably in the range of about 2–8%. Other additives, such as, forexample, polymer fillers, metallic fillers, and/or organic and inorganicfillers (e.g. polymers, balata, ionomers, etc.) may be added as well toincrease the specific gravity of the polyurethane material. The entiremixture is preferably agitated in the mixing chamber in the range ofabout 1 to 250 rpm prior to molding. A more detailed explanation of oneaspect of the process is set forth in U.S. Pat. No. 6,200,512, entitledGolf Balls And Methods Of Manufacturing The Same, filed on Apr. 20,1999, assigned to Callaway Golf Company, and which is herebyincorporated by reference in its entirety. A more detailed explanationof the casting system is set forth in U.S. Pat. No. 6,395,218, entitledMethod For Forming A Thermoset Golf Ball Cover, filed on Feb. 1, 2000,assigned to Callaway Golf Company, and which is hereby incorporated byreference in its entirety.

The core 12 of the golf ball 10 is generally composed of a blend of abase rubber, a cross-linking agent, a free radical initiator, and one ormore fillers or processing aids. A preferred base rubber is apolybutadiene having a cis-1,4 content above 90%, and more preferably98% or above.

The use of cross-linking agents in a golf ball core is well known, andmetal acrylate salts are examples of such cross-linking agents. Forexample, metal salt diacrylates, dimethacrylates, or mono(meth)acrylatesare preferred for use in the golf ball cores of the present invention,and zinc diacrylate is a particularly preferred cross-linking agent. Acommercially available suitable zinc diacrylate is SR-416 available fromSartomer Co., Inc., Exton, Pa. Other metal salt di- ormono(meth)acrylates suitable for use in the present invention includethose in which the metal is calcium or magnesium. In the manufacturingprocess it may be beneficial to pre-mix some cross-linking agent(s),such as, e.g., zinc diacrylate, with the polybutadiene in a master batchprior to blending with other core components.

Free radical initiators are used to promote cross-linking of the baserubber and the cross-linking agent. Suitable free radical initiators foruse in the golf ball core 12 of the present invention include peroxidessuch as dicumyl peroxide, bis-(t-butyl peroxy) diisopropyl benzene,t-butyl perbenzoate, di-t-butyl peroxide,2,5-dimethyl-2,5-di-5-butylperoxy-hexane, 1,1-di (t-butylperoxy)3,3,5-trimethyl cyclohexane, and the like, all of which are readilycommercially available.

Zinc oxide is also preferably included in the core formulation. Zincoxide may primarily be used as a weight adjusting filler, and is alsobelieved to participate in the cross-linking of the other components ofthe core (e.g. as a coagent). Additional processing aids such asdispersants and activators may optionally be included. In particular,zinc stearate may be added as a processing aid (e.g. as an activator).Any of a number of specific gravity adjusting fillers may be included toobtain a preferred total weight of the core 12. Examples of such fillersinclude tungsten and barium sulfate. All such processing aids andfillers are readily commercially available. One tungsten filler is WP102Tungsten (having a 3 micron particle size) available from AtlanticEquipment Engineers of New Jersey.

Table One below provides the ranges of materials included in thepreferred core formulations of the present invention.

Table One Component Preferred Range Most Preferred Range Polybutadiene100 parts 100 parts Zinc diacrylate 20–35 phr 25–30 phr Zinc oxide  0–50phr  5–15 phr Zinc stearate  0–15 phr  1–10 phr Peroxide 0.2–2.5 phr0.5–1.5 phr Filler As desired As desired (e.g. tungsten) (e.g. 2–10 phr)(e.g. 2–10 phr)

In the present invention, the core components are mixed and compressionmolded in a conventional manner known to those skilled in the art. In apreferred form, the finished core 12 has a diameter of about 1.35 toabout 1.64 inches for a golf ball 10 having an outer diameter of 1.68inches. The core weight is preferably maintained in the range of about32 to about 40 g. The core PGA compression is preferably maintained inthe range of about 50 to 90, and most preferably about 55 to 80.

As used herein, the term “PGA compression” is defined as follows: PGAcompression value=180—Riehle compression value. The Riehle compressionvalue is the amount of deformation of a golf ball in inches under astatic load of 200 pounds, multiplied by 1000. Accordingly, for adeformation of 0.095 inches under a load of 200 pounds, the Riehlecompression value is 95 and the PGA compression value is 85.

If the golf ball 10 has a boundary layer 14, the boundary layer 14 ispreferably composed of a thermoplastic material. Suitable thermoplasticmaterials for the boundary layer 14 include: HYTREL® and/or HYLENE®products from DuPont, Wilmington, Del.; PEBAX® products from ElfAtochem, Philadelphia, Pa.; SURLYN® products from DuPont; and/or ESCOR®or IOTEK® products from Exxon Chemical, Houston, Tex.

The Shore D hardness of the boundary layer 14 preferably ranges from 50to 75, as measured according to ASTM D-2290. In a most preferredembodiment, the boundary layer 14 has a Shore D hardness in the range of58–65. One reason for preferring a boundary layer 14 with a Shore Dhardness of 75 or lower is to improve the feel of the resultant golfball. It is also preferred that the boundary layer 14 is composed of ablend of SURLYN® ionomer resins.

SURLYN® 8150, 9150, and 6320 are, respectively, an ionomer resincomposed of a sodium neutralized copolymer of ethylene and methacrylicacid, an ionomer resin composed of a zinc neutralized copolymer ofethylene and methacrylic acid, and an ionomer resin composed of aterpolymer of ethylene, methacrylic acid and n-butyl acrylate partiallyneutralized with magnesium. The optional boundary layer 14 is preferablycomposed of a blend of these ionomers.

One formulation for the optional boundary layer 14 has 25–50 weightpercent SURLYN 8150, 25–50 weight percent SURLYN 9150, and 25–50 weightpercent SURLYN 6320. Another formulation for the optional boundary layer14 has 25–75 weight percent SURLYN 9150, and 25–75 weight percent SURLYN6320. Those skilled in the pertinent art will recognize that otherionomers may be utilized for the optional boundary layer 14 withoutdeparting from the scope and spirit of the present invention. The ShoreD hardness of the boundary layer 14 is preferably 50 to 75, morepreferably from 55–65 Shore D, and most preferably 58–63 Shore D, asmeasured according to ASTM-D2240.

The polyurethane material of the present invention preferably has aShore D hardness ranging from 30 to 60 as measured according toASTM-D2240, more preferably 40 to 55 Shore D, and most preferably 50Shore D.

One formulation for the polyurethane material of the present inventionis polytetramethylene ether glycol terminated toluene diisocyanateprepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to 75 partsper one hundred parts of the curative blend andN,N′-bis-alkyl-p-phenylenediamine in an amount of 25 to 75 parts per onehundred parts of the curative blend, and 1 to 10 parts of a triol suchas trimetholylpropane (“TMP”).

Another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 50 parts per onehundred parts of the curative blend andN,N′-bis-alkyl-p-phenylenediamine in an amount of 50 parts per onehundred parts of the curative blend, and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polyether terminated toluene diisocyanate prepolymer (NCOcontent of 6%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 55 parts per onehundred parts of the curative blend andN,N′-bis-alkyl-p-phenylenediamine in an amount of 45 parts per onehundred parts of the curative blend, and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 65 parts per onehundred parts of the curative blend andN,N′-bis-alkyl-p-phenylenediamine in an amount of 35 parts per onehundred parts of the curative blend, and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to 75 partsper one hundred parts of the curative blend andN,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediaminein an amount of 25 to 75 parts per one hundred parts of the curativeblend, and 1 to 10 parts of a triol such as trimetholylpropane (“TMP”).

Another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 50 parts per onehundred parts of the curative blend andN,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediaminein an amount of 50 parts per one hundred parts of the curative blend,and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polyether terminated toluene diisocyanate prepolymer (NCOcontent of 6%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 55 parts per onehundred parts of the curative blend andN,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediaminein an amount of 45 parts per one hundred parts of the curative blend,and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 65 parts per onehundred parts of the curative blend andN,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediaminein an amount of 35 parts per one hundred parts of the curative blend,and 3 parts TMP.

Yet another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (NCO content of 5%), a curative blend comprising4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 25 to 75 partsper one hundred parts of the curative blend and an aliphatic diamine inan amount of 25 to 75 parts per one hundred parts of the curative blend,and 1 to 10 parts of a triol such as trimetholylpropane (“TMP”).

Yet another formulation for the polyurethane material of the presentinvention is polytetramethylene ether glycol terminated hexamthylenediisocyanate prepolymer (NCO content of 11%), a curative blendcomprising 4,4′-methylenebis-(2,6-diethyl)-aniline in an amount of 10 to90 parts per one hundred parts of the curative blend and an aliphaticdiamine in an amount of 10 to 90 parts per one hundred parts of thecurative blend.

Yet another formulation for the polyurethane material of the presentinvention is an aromatic polyurethane prepolymer, and a curative blendcomprising an aromatic curative (such as4,4′-methylenebis-(2,6-diethyl)-aniline) in an amount of 10 to 90 partsper one hundred parts of the curative blend and an aliphatic curative(such as an aliphatic diamine) in an amount of 10 to 90 parts per onehundred parts of the curative blend.

Yet another formulation for the polyurethane material of the presentinvention is an aliphatic polyurethane prepolymer, and a curative blendcomprising an aromatic curative in an amount of 10 to 90 parts per onehundred parts of the curative blend and an aliphatic curative in anamount of 10 to 90 parts per one hundred parts of the curative blend.

The preferred construction of a golf ball 10 utilizing the polyurethanematerial of the present invention is a three-piece solid golf ballhaving a solid polybutadiene core 12, a boundary layer 14 composed of ablend of ionomers, and a cover 16 composed of the polyurethane materialof the present invention. The core 12 is preferably compression molded,the boundary layer 14 is preferably injection molded, and the cover 16is preferably cast. The golf ball 10 may be finished with one or twolayers of a base white coating, a clear coating and an indicia.

The thickness of the cover 16 preferably ranges from 0.010 inch to 0.070inch, more preferably ranges from 0.010 inch to 0.050 inch, evenpreferably ranges from 0.010 inch to 0.044 inch, most preferably rangesfrom 0.025 inch to 0.040 inch, and is most preferably 0.025 inch. Theboundary layer 14 is preferably injection molded and preferably rangesin thickness from 0.040 inch to 0.090 inch, more preferably from 0.045inch to 0.070 inch, and most preferably from 0.050 inch to 0.060 inch.The boundary layer 14 may also be compression molded from half shells.The core 12 preferably has a diameter of between 1.35 inches and 1.60inches, more preferably between 1.45 inches and 1.55 inches, and mostpreferably 1.49 inches. The core 12 preferably has a PGA compressionranging from 70–110 points, and most preferably 100 points. A moredetailed description of a construction and performance properties of agolf ball utilizing the polyurethane material of the present inventionis set forth in U.S. Pat. No. 6,443,858, for a Golf Ball With A HighCoefficient Of Restitution, issued on Sep. 2, 2002, assigned to CallawayGolf Company, and U.S. Pat. No. 6,478,697 for a Golf Ball With A HighCoefficient Of Restitution, filed on Nov. 12, 2002, assigned to CallawayGolf Company, both of which are hereby incorporated by reference intheir entireties.

The Shore D hardness of the golf ball 10, as measured on the golf ball,is preferably between 40 Shore D points to 75 Shore D points, and mostpreferably between 50 Shore D points and 65 Shore D points. The hardnessof the golf ball 10 is measured using an Instron Shore D Hardnessmeasurement device wherein the golf ball 10 is placed within a holderand the pin is lowered to the surface to measure the hardness. Theaverage of five measurements is used in calculating the ball hardness.The ball hardness is preferably measured on a land area of the cover 14.The preferred overall diameter of the golf ball 10 is approximately 1.68inches, and the preferred mass is approximately 45.5 grams. However,those skilled in the pertinent art will recognize that the diameter ofthe golf ball 10 may be smaller (e.g. 1.65 inches) or larger (e.g. 1.70inches) without departing from the scope and spirit of the presentinvention. Further, the mass may also vary without departing from thescope and spirit of the present invention.

The surface geometry of the golf ball 10 is preferably a conventionaldimple pattern such as disclosed in U.S. Pat. No. 6,213,898 for a GolfBall With An Aerodynamic Surface On A Polyurethane Cover, whichpertinent parts are hereby incorporated by reference. Alternatively, thesurface geometry of the golf ball 10 may have a non-dimple pattern suchas disclosed in U.S. Pat. No. 6,290,615 filed on Nov. 18, 1999 for AGolf Ball Having Tubular Lattice Pattern, which pertinent parts arehereby incorporated by reference.

The flexural modulus of the thermosetting polyurethane cover material ofthe present invention, as measured according to ASTM D790, preferablyranges from 7,000 pounds per square inch (“psi”) to 35,000 psi, morepreferably from 10,000 psi to 25,000 psi, and even more preferably from18,000 psi to 22,000 psi.

The polyurethane material of the present invention provides a golf ballcover 16 with greater durability than most other polyurethane covers.Cover durability is determined according to the following procedure. ACALLAWAY GOLF®STEELHEAD™ X-14® PRO SERIES sand wedge was used on a GOLFLABS robot to strike twelve golf balls per sample twice (the balls werehit on each side) and to strike six control golf balls twice. The golfball is placed on a tee with the pole positioned for impact with theclub. The impact area is sprayed with water. The robot is triggered, theclub is swung at approximately 72 miles per hour, and the wet golf ballis struck. The golf ball retrieved and placed on the tee with theopposite side of the pole positioned for impact and sprayed with water.The robot is triggered and the wet golf ball is again struck. The clubface and grooves of the sand wedge are cleaned and dried prior to eachhit. The golf ball is retrieved and examined under a stereoscopicmicroscope for evaluation and ranking. The results are analyzed usingstatistics with a 95% confidence level.

The cover durability is ranked according to the following criteria:

1 Portion of cover has been completely sheared off. Dimples (or othersurface geometry) have been reduced or greatly removed;

2 Cover material has been sheared to the extent that flaps of cover arevisible, but not severe enough to completely shear off and removedimples;

3 Moderate cutting of the cover material is evident to the extent thatinternal portions of the cover are exposed, but the cover is stillintact;

3.5 Slight cutting of the cover material is evident with little or nointernal portions of the cover exposed, bunching of the cover isapparent from a side or profile view;

3.75 Slight cutting of the cover material is evident with little or nointernal portions of the cover exposed, and no bunching of the cover isapparent from a side or profile view;

4 Indentations in the cover are evident, but there is no bunching of thecover material;

4.5 Groove marks are clearly defined, but no deformation of the covermaterial is apparent;

5 Groove marks are difficult to see and slight score marks may bevisible, but the finish is not cracked or broken and there is no damageto the cover material.

Golf balls utilizing the polyurethane material of the present inventionwere compared to the CALLAWAY GOLF® CTU30™ BLUE golf ball, the CALLAWAYGOLF® CTU30™ RED golf ball, the TITLEIST®PROV1™ golf ball and theMAXFLI® A10 golf ball, all of which have thermosetting polyurethanecovers. The CTU30™ RED golf ball had a 2.42 ranking, the CTU30™ BLUEgolf ball had a 2.69 ranking, the PROV1™ golf ball had a 2.63 rankingand the A10™ golf ball had a 2.58 ranking. The golf balls that utilizedthe polyurethane cover of the present invention had a ranking rangingfrom 2.89 to 3.34.

From the foregoing it is believed that those skilled in the pertinentart will recognize the meritorious advancement of this invention andwill readily understand that while the present invention has beendescribed in association with a preferred embodiment thereof, and otherembodiments illustrated in the accompanying drawings, numerous changes,modifications and substitutions of equivalents may be made thereinwithout departing from the spirit and scope of this invention which isintended to be unlimited by the foregoing except as may appear in thefollowing appended claims. Therefore, the embodiments of the inventionin which an exclusive property or privilege is claimed are defined inthe following appended claims.

1. A golf ball comprising: a core; and a cover formed over the core, thecover composed of a thermosetting polyurethane material formed fromreactants comprising a polytetramethylene ether glycol terminatedhexamethylene diisocyanate prepolymer to having a NCO group contentranging from 8.0% to 12.0% at least one polyurethane prepolymer and acurative blend comprising 4,4′-methylenebis-(2,6-diethyl)-aniline), anda second curing agent selected from the group consisting ofN,N′-bis-alkyl-p-phenylenediamine, N,N′-dialkylamino-diphenylmethanewith tetrapropoxylated ethylenediamine, and an aliphatic diamine, andtrimetholylpropane in an amount of 1 to 10 parts per one hundred partsof the amines in the curative blend; wherein the cover has a thicknessranging from 0.010 inch to 0.044 inch.
 2. The golf ball according toclaim 1 further comprising at least one boundary layer disposed betweenthe core and the cover.
 3. The golf ball according to claim 2 whereinthe boundary layer is composed of a blend of ionomers.
 4. A golf ballcomprising: a core comprising a polybutadiene mixture; a boundary layerformed over the core; and a cover formed over the boundary layer, thecover composed of a thermosetting polyurethane material formed fromreactants comprising at least one polyurethane prepolymer and a curativeblend comprising trimetholylpropane in an amount of 1 to 10 parts perone hundred parts of the amines in the curative blend,4,4′-methylenebis-(2,6-diethyl)-aniline) in an amount of 75 parts perone hundred parts of the amines in the curative blend and an aliphaticdiamine in an amount of 25 parts per one hundred parts of the amines inthe curative blend.
 5. A golf ball comprising: a core comprising apolybutadiene mixture, the core having a diameter ranging from 1.35inches to 1.64 inches and having a PGA compression ranging from 50 to90; a boundary layer formed over the core, the boundary layer composedof a blend of ionomer materials, the boundary layer having a thicknessranging from 0.020 inch to 0.075 inch, the blend of ionomer materialshaving a Shore D hardness ranging from 50 to 75 as measured according toASTM-D2240; and a cover formed over the boundary layer, the covercomposed of a thermosetting polyurethane material formed from reactantscomprising at least one polyurethane prepolymer and a curativecomprising trimetholylpropane in an amount of 1 to 10 parts per onehundred parts of the amines in the curative blend,4,4′-methylenebis-(2,6-diethyl)-aniline) and a second curing agentselected from the group consisting of N,N′-bis-alkyl-p-phenylenediamine,N,N′-dialkylamino-diphenylmethane with tetrapropoxylated ethylenediamineand an aliphatic diamine, wherein the thermosetting polyurethanematerial has a Shore D hardness ranging from 30 to 60 as measuredaccording to ASTM-D2240, and a thickness ranging from 0.010 inch to0.044 inch.
 6. A golf ball comprising: a core comprising a polybutadienemixture; a boundary layer formed over the core; and a cover formed overthe boundary layer, the cover composed of a thermosetting polyurethanematerial formed from reactants comprising at least one aliphaticpolyurethane prepolymer and a curative blend comprisingtrimetholylpropane in an amount of 1 to 10 parts one hundred parts ofthe amines in the curative blend, an aromatic curative amine in anamount of 10 to 90 parts per one hundred parts of the amines in thecurative blend and an aliphatic amine curative in an amount of 10 to 90parts per one hundred parts of the amines in the curative blend.
 7. Thegolf ball according to claim 6 wherein the thermosetting polyurethanematerial has a flexural modulus ranging from 10,000 psi to 25,000 psiwhen measured according to ASTM D790.
 8. The golf ball according toclaim 6 wherein the cover has a thickness ranging from 0.010 inch to0.044 inch.
 9. The golf ball according to claim 6 wherein the curativeblend comprises an aromatic curative in an amount of 50 to 75 parts perone hundred parts of the curative blend and an aliphatic curative in anamount of 25 to 50 parts per one hundred parts of the curative blend.10. A golf ball comprising: a core comprising a polybutadiene mixture,the core having a diameter ranging from 1.35 inches to 1.64 inches andhaving a PGA compression ranging from 50 to 90; a boundary layer formedover the core, the boundary layer composed of a blend of ionomermaterials, the boundary layer having a thickness ranging from 0.020 inchto 0.075 inch, the blend of ionomer materials having a Shore D hardnessranging from 50 to 75 as measured according to ASTM-D2240; and a coverformed over the boundary layer, the cover composed of a thermosettingpolyurethane material formed from reactants comprising at least onealiphatic polyurethane prepolymer and a curative blend comprisingtrimetholylpropane in an amount of 1 to 10 parts per one hundred partsof the amines in the curative blend, an aromatic amine curative in anamount of 10 to 90 parts per one hundred parts of the amines in thecurative blend and an aliphatic amine curative in an amount of 10 to 90parts per one hundred parts of the amines in the curative blend, whereinthe thermosetting polyurethane material has a Shore D hardness rangingfrom 30 to 60 as measured according to ASTM-D2240, and a thicknessranging from 0.010 inch to 0.044 inch.
 11. A golf ball comprising: acore comprising a polybutadiene mixture, the core having a diameterranging from 1.35 inches to 1.64 inches and having a PGA compressionranging from 50 to 90; a boundary layer formed over the core, theboundary layer composed of a blend of ionomer materials, the boundarylayer having a thickness ranging from 0.020 inch to 0.075 inch, theblend of ionomer materials having a Shore D hardness ranging from 50 to75 as measured according to ASTM-D2240; and a cover fanned over theboundary layer, the cover composed of a thermosetting polyurethanematerial formed from reactants comprising at least one aromaticpolyurethane prepolymer and a curative blend comprisingtrimetholylpropane in an amount of 1 to 10 parts per one hundred partsof the amines in the curative blend, an aromatic amine curative in anamount of 10 to 90 parts per one hundred parts of the amines in thecurative blend and an amine aliphatic curative in an amount of 10 to 90parts per one hundred parts of the amines in the curative blend, whereinthe thermosetting polyurethane material has a Shore D hardness rangingfrom 30 to 60 as measured according to ASTM-D2240, and a thicknessranging from 0.010 inch to 0.044 inch.